Textile bleaching composition



3,163,606 TEXTILE BLEACHING COMPOSITION Wilheimus J. C. Viveen andCorneiis U. Kloosterman,

Deventer, Netheriands, assignors to Koninklijke Industrieele Maatschappyvorheen Notary 8: van der Lande N.V., Deventer, Netherlands, acorporatien of the Netherlands No Drawing. Filed June 2, 1969, Ser. No.33,3?7 Claims priority, application Great Britain, June 19, 1959,21,220/59; July 29, 1959, 26,061/59; Oct. 13, E59, 34,695/59;Netherlands, June '6, 1959, 239,952.

Claims. (Cl. 252-98) This invention relates to a Washing and/orbleaching composition containing, in addition to an active oxygenreleasing compound, an activator for this compound, and further to aprocess of washing and bleaching textiles with the aid of suchcompositions, and further to certain novel activator compounds for usein said compositions.

It is an object of this invention to provide washing and bleachingcompositions containing active oxygen releasing compounds and activatorsfor such compounds.

It is a further object of this invention to provide certain novelcompounds and mixtures of said compounds for use as activators foractive oxygen releasing compounds in washing and bleaching compositions.

It is a further object of this invention to provide a process forproducing said novel activator compounds.

It is a further object of this invention to provide said activatorcompounds in a coated form to enhance the activity and stability of saidcompounds.

Further objects and attendant advantages of this invention will becomeapparent from the following more detailed description.

The term textiles as used throughout the specification is intended toinclude natural and synthetic fibres as well as products manufacturedtherefrom or therewith.

It is well-known that on Washing and/or bleaching textiles use is madeof agents containing active oxygen releasing compounds having ableaching elfect on the textiles to be treated. As the active oxygenreleasing compounds, inorganic persalts such as perborates,percarbonates, perphosphates, persilicates, persulphates and, moreover,hydrogen peroxide and sodium peroxide are used.

However, washing and/or bleaching agents containing such active oxygenreleasing compounds generally have the disadvantage that their bleachingeffect is relatively low at temperatures below 85 C. which gives rise todifficulties when these agents are used in machines for householdpurposes in which the temperature of the washwater is not higher thanabout 70 C.

It has already been proposed to enhance theeifect of a washing and/orbleaching agent containing an active oxygen releasing compound by addingthereto particular substances, so-called activators. Definite quantitiesof organic acid anhydrides, for instance, have been added to washing andbleaching agents containing active oxygen nited States Patent 0 ice ' ishightly eflicient for the washing and/ or bleaching treatment oftextiles at a temperature below boiling temperature.

Consequently, this invention relates in part to a Washing and/ orbleaching composition containing besides an active oxygen releasingcompound an activator for this compound. and is characterized in that acompound-containing one or more nitrogen atoms having at least twoacylgroups attached to the same nitrogen atom or amixture of suchcompounds, is used as the activator.

The bleaching elfect of the compositions according to the invention is,when using them at temperatures below boiling temperature, especially attemperatures between 15 and 85 (3., not only considerably better thanthe eiiect obtained at the same temperature with compositions notcontaining an activator according to the invention, but furthermore alsogreater than the effect of compositions without activators at boilingtemperature. Moreover, the compositions according to the invention causeconsiderably less loss in strength of the fibres, do not' significantlyaffect cellulose and synthetic fibres such as polyamide fibres, whilefurthermore the drawbacks associated with the use of the agents hithertoknown for washing coloured material are practically fully eliminated,especially as regards the attack of the colour, if the agents accordingto the invention are used for this purpose. Apart from this, thecompositions according to the invention are particularly effective forwashing cotton goods,

as this material even if washed several times keeps a high degreeoflightness and does not easily become yellow. The bleachingcompositions according to the invention and especially the compositionscontaining perborate possess, moreover, the additional advantage thatwith a favourable ratio of perborate and activator an overbleaching isnot possible. Furthermore, these bleaching compositions are excellentlysuitable for addition to the rinsing bath.

As activators for oxygen releasing compounds accordingto this inventionthere are included: N-diacylated amines, e.g., diacetylmethylarm'ne,diacetylethylamine, diacetylpropylamine, diacetylbutylamine,diacetylbenzylamine'and diacetylaniline; N-diacylated ammonia, e.g.,diacetamide, dipropionamide; N-diacylated amides, e.g., Nformyldiacetamide, N acetyldiacetamide, (triaceta-- mide),N-propionyldiacetamide, N-butyryldiacetamide, N-valeryldiacetamide,N-caproyldiacetamide, di-carboxsuccinimide; N,N-diacety1cyanamide;N-diacylated urereleasing compounds. However, in practice, this measurea does not yield the desired result, as the reactivity of most acidanhydrides appears to be insuificient in this respect.

It has also been proposed to add formamide and retire-- sentatives ofthe nitrile group to washing agents containing active oxygen releasingcompounds. However, formamide is a liquid and it is diflicult toincorporate it into a washing powder. The result obtained by addingformamide or nitriles is moreover very small.

Now it has been found that if a compound containing one or more nitrogenatoms having at least two acyl groups attached to the same nitrogen atomor a mixture of such compounds is added to a washng and/oibleachingagent of the usual composition containing an active oxygen releasingcompound, a composition is obtained which thanes, e.g.,N,N-diacetylethylurethane, N-acetyLN-propionylethylurethane;N-diacetylated hydrazines, e.g., tri. acetylhydrazine,tetra-acetylhydrazine, tripfopionylhydrazine,N,N-diacetyl-N-benzoylhydrazine and N,Ndiacetyl-N'-isopropylidenehydrazine; N-diacylated alkylenediamines, e.g.,triacetylmethylenediamine,- tetra-acetylmethylenediamine,hexamethylenediamine and tetra-acetylphenylenediamine,

bazide and dicyanodiamide. :f I

The favourable properties mentioned above of the washing and/orbleaching agents according to the invention the 'N-diacyl compounds ofsemicarbazide, thiosemicar:

may surprisingly still be improved to a large extent, if the activatoraccording to the invention iscovered with a solid material soluble inthe washing and/ or bleaching liquid. j As such, stearic acid,polyethyleneglycol such as, e.g.,' Carbowax 4000 and 6000 (Carbow ax isaregisteredtrademark in the name of Union Carbide Corporation relating topolyethylene glycols. Carbowax 40(30and 6000is the I designation givensolid polyethylene glycols having re "spectively an average molecularweight] of 39004 and 6000-7500 Furthermore condensation products ofethyleneoxide and propyleneoxide may be used. Morepartetra-acetylethylenediamine, tetra-'acetyh' ticularly those compoundshaving a useful function in the suds, such as, e.g., polyvinylalcohol,carboxymethylcellulose, cetylalcohol and fatty acid alkanolamides, areespecially suitable. Moreover, by this means the shelf life, especiallyof the finished powders, is enhanced.

It is recommended to granulate the activator before covering.

Covering may be effected in coating-pans suitable to the purpose. Thecovering material dissolved in water or in an organic solvent, issprayed on the activator in finely divided form, after which the coveredmaterial is dried. Solutions of stearic acid, Carbowax or C -Cisopropanolamide in isopropanol as well as solutions of polyvinylalcoholand carboxymethylcellulose in diluted ethanol are very suitable. As tothe quantity of the covering to be used, it is in general sufficient toapply 1 to 30% by weight on the activator.

Washing and/ or bleaching of textiles may be effected with the aid of aliquid containing the finished products according to the invention.

However, it is also possible to execute this treatment with a washing orbleaching liquid to which one or more activators have been added, justprior to the treatment or during the same.

In any case very good results are obtained with a treatment temperaturebelow boiling temperature, preferably however with a temperature between15 and 85 C.

As activators for the active oxygen releasing compound in a washingand/or bleaching agent there have been found especially effective thehitherto unknown compounds with the general formula CH3C O C C113 inwhich R represents a hydrogen-atom or a COCH group.

These new compounds according to the invention, or mixtures thereof, maybe obtained by either of the following two methods.

Thus it is possible to prepare N,N,N'N'-tetraacetylmethylenediamine byallowing to react ketene on a mixture of N,N-diacetylmethylenediamineand an inert solvent in the presence of an acid-reacting catalyst.

This reaction may be executed in benzene as an inert solvent at atemperature of 30-80 C., preferably however at a temperature of 5065 C.,in the presence of 0.53%, preferably of 2% by weight of ptoluenesulphonic acid calculated on N,N-diacetylmethylenediamine. TheN,N,NN-tetra-acetyhnethylenediamine formed may be recovered from thereaction mixture in any conventional way.

According to the invention, N,N,NN'-tetra-acetyl methylenediamine may,however, also be obtained by acetylating N,N-diacetylmethylenediaminewith the aid of acetic acid anhydride while eliminating continuously theacetic acid formed during the reactioin, e.g., by distillation.

If during the reaction between diacetylmethylenediamine and acetic acidanhydride, the acetic acid liberated is not eliminated from the reactionmixture, mainly N,N,N-triacetylmethylenediamine is formed.

When only part of the quantity of acetic acid that theoretically couldbe formed during the acetylation is eliminated from the reactionmixture, mixtures are obtained that appearto containtriacetylmethylenediamine and tetra-acetylmethylenediamine with thequantity of the former increasing as less acetic acid is eliminated.

The following examples are presented to further illustrate theinvention, and should not be considered as limiting thereof.

EXAMPLE I Pieces of cotton fabric were soiled with the juice of blackcurrants, by evenly applying to them 2.7 cc., of black currant juice per100 cm. of surface of cotton fabric d by means of a brush. After beingdried in the air, the lightness of the fabric was measured with aphotoelectric remission meter. It was 29% of the lightness of magnesiumoxide. 7

Parts of the pieces of material were washed for 15 minutes at 60 in sudsof the following composition:

G./l. Sodium salt of dodecyl benzene sulphonic acid 0.85 Laurylisopropanolamide 0.10 Tetrasodium pyrophosphate 0.75 Pentasodiumtripolyphosphate 0.60 Alkaline water-glass (Na O/SiO =l/2) 0.20 Na CMC(sodium carboxymethylcellulose) 0.04 Sodium sulphate 0.80 Sodiumperborate-tetrahydrate (10.2% active oxygen) 0.50

The percentage of lightness of the washed pieces of material amounted to64 (lightness of magnesium oxide=100 units), which is 13 units higherthan the percentage of lightness of the pieces of material afterthorough rinsing with water, which was 51.

Other parts of the material were Washed in three samples of suds of thesame composition, to which respectively 0.1, 0.4 and 0.5 g./l. oftetra-acetyl hydrazine was added. These suds contained per atom ofactive oxygen from the perborate 0.63, 2.50 and 3.14 acetyl groups astetra-acetyl hydrazine, respectively.

The percentages of lightness of the thus washed material wererespectively 20, 31 and 34 units higher than the percentage of lightnessof the material which was only thoroughly rinsed with water. Therelative improvements by adding tetra-acetyl hydrazine in theconcentrations mentioned were therefore 54%, 138% and 162%.

EXAMPLE II Pieces of the same kind of fabric, soiled with black currantjuice, as used in Example I, were washed for 15 minutes at 60 C. in sudsof the following composition:

G./l. Sodium soap 3.1T Sodium carbonate 1.00 Neutral water-glass (NaO/SiO =1/3.3) 0.17 Sodium perborate-tetrahydrate (9.9% of active oxygen)0.68

The percentage of lightness of the material was increased to 62% bywashing (lightness of magnesium oxide=100 unit); this is 11 units higherthan the lightness obtained by only rinsing the material thoroughly withwater.

If the suds also contained 0.42 g./1. of tetra-acetyl hydrazine, thepercentage of lightness of the material was increased to 73, which is 22units more than the percentage of lightness obtained after thoroughlyrinsing with water only. The relative improvement by adding tetra-acetylhydrazine therefore amounted to 100%. In this case, the number of acetylgroups added to the suds as tetra-acetyl hydrazine was 2.0 per atom ofactive oxygen from the perborate.

EXAMPLE III A detergent in powder form had the following composition:

100 parts by weight of this powder were mixed with 8 parts by weight ofsodium perborate-tetrahydrate and 6.25 parts by weight of tetra-acetylhydrazine (STAH mixture).

A solution was prepared, containing 5.70 g./l. of the STAH mixture andpieces of the same kind of material stained with fruit juice, as used inExample I, were washed in this solution for 15 minutes at 60 C.

The material was then rinsed three times, ironed with a hot iron and thelightness was measured with a Hunter photoelectric remission meter.

With this test, a similar test was carried out with a mixture of 100parts by weight of the afore-mentioned powder and 8 parts by weight ofsodium perboratetetrahydrate without tetra-acetyl hydrazine (mixtureSO). 5.4 grams per litre solution were used of this mixture.

The lightness of the material washed with STAH mixture was 27 unitshigher than the lightness of material thoroughly rinsed with water only(51 units).

In the case of the SO mixture, this difference in lightness was 12 units(lightness of magnesium oxide=100 units).

So by using a quantity of tetra-acetyl hydrazine such as to correspondto 2.5 bound acetyl groups per atom of active oxygen, 21 relativeimprovement of 125% was obtained.

EXAMPLE IV 100 parts by weight of the powder described in Example HIWere mixed with 8 parts of sodium perboratetetrahydrate and 6.60 partsof triacetyl hydrazine (STrAH mixture).

A solution was prepared containing 5.75 g. per litre of this STrAHmixture and the same washing test was carried out with it as describedin Example III.

The lightness of the material was 22 units higher than the lightness ofthe material rinsed with water thoroughly (51 units). In the case of theSO mixture, this difierence in lightness was 12 units.

So the relative improvement in this case, where 2.5 bound acetyl groupsper atom of active oxygen were used, was 83%.

EXAMPLE V 100 parts by weight of the powder described in Example IIIwere mixed with 8 parts of sodium perboratetetrahydrate and 11.0 partsof tripropionyl hydrazine (STrPrH mixture).

A solution was prepared, containing 5.95 g. per litre of this STrPrHmixture and a similar washing test was carried out with it as describedin Example III, except that in this case the experiment Was carried outat 50 C.

The lightness of the washed material was 23 units higher than thelightness of material rinsed thoroughly with water (51 units). In thecase of the SO mixture, this diiference in lightness was 12 units.

So the relative improvement in this case, where 3.3 bound propionylgroups per atom of active oxygen were used, was 92%.

EXAMPLE VI 100 parts by weight of the powder described in Example IIIwere mixed with 8 parts of sodium perboratetetrahydrate and 7.05 partsof tetra-acetylethylenediamine (STAED mixture).

A solution was prepared, containing 5.75 g. per litre of this STAEDmixture and a similar washing test was carried out with it as describedin Example III, except that another lot of cotton fabric, soiled withblack currant juice, was used. a

The lightness of the washed material was 23 units higher than thelightness of material rinsed thoroughly with water (51 units). In thecase of the SO mixture, this difference in lightness was 13 units.

So the relative improvement in this case, where 2.5

bound acetyl groups per atom of active oxygen were used, was 77% EXAMPLEV11 100 parts by weight of the powder described in Example III weremixed with 8 parts of sodium perboratetetrahydrate and 6.31 parts ofdiacetamide (SDAA mixture).

A solution was prepared, containing 5.72 g. per litre of this SDAAmixture and a similar washing testwas carried out with it as describedin Example VI.

The lightness of the washed material was 22 units higher than thelightness of material rinsed thoroughly with water (51 units). In thecase of the SO mixture, this difference in lightness was 13 units.

So the relative improvement in this case, where 2.5 bound acetyl groupsper atom of active oxygen were used, was 69%. 1

EXAMPLE VIII 100 parts by weight of the powder described in Ex-' ampleIII were mixed with 8 parts of sodium perboratetetrahydrate and 5.96parts of triacetamide (STrAArnixture).

A solution was prepared containing 5.70 g. per litre of this STrAAmixture and a similar washing test Was I carried out with it asdescribed in Example VI.

The lightness of the washed material was 30 units higher than thelightness of material rinsed thoroughly with water (51 units). In thecase of the SO mixture, this difference in lightness was 13 units.

So the relative improvement in this case, where 2.5 bound acetyl groupsper atom of active oxygen were used, was 131%.

EXAMPLE D A detergent in powder form had the following composition:

of sodium soap of sodium carbonate of neutral water-glass of water Withthis test, a similar test was carried outwith a mixture of 100 parts byweight of the afore-mentioned powder and 7.5 parts by weight of sodiumperbroratetetrahydrate without diacetyl propylarnine (ZO mixture). 8.60grams per litre of this mixture were used.

' The lightness of thematerial washed with the ZDAPrA mixture was 19units higher than the lightness of material thoroughly rinsed with wateronly (51 units).

In the case of the Z0 mixture, this diiierence in lightness was 12 units(lightness of magnesium oxide=100 units). 7'

So by using a quantity of diacetyl propylamine such as to correspond to2.0 bound acetyl groups per atom of active oxygen, a relativeimprovement of 58% was obtained. V a

' EXAMPLE X 100 parts by weight of the powder described Example DC weremixed with 7 .5 parts by Weight of sodiumperborate-tetrahydrate and 8.35parts by weight of diacetanilide (ZDAAL mixture).

A solution was prepared containing 9.30 g. per litre of 7 this ZDAALmixture and a similar washing test was carried out with it as describedin Example IX.

The lightness of the material washed with the ZDAAL mixture was 23 unitshigher than the lightness of material thoroughly rinsed wtih water only(51 units). In the case of the Z mixture, this difference in lightnesswas 12 units.

So the relative improvement in this case, where 2.0 bound acetyl groupsper atom of active oxygen were used, was 92% EXAMPLE XI A similarwashing test, as described in Example I, was carried out using sudscontaining 513 mg. N-ethyldiacetamide per litre instead of tetra-acetylhydrazine.

The relative improvement as to the lightness of the washed material wasin the case, where 2.5 bound acetyl groups per atom of active oxygenwere used, 125%.

EXAMPLE XII A similar washing test as described in Example II wascarried out using suds containing 724 mg. N,N-diacetyl urethane perlitre instead of tetra-acetyl hydrazine.

The relative improvement as to the lightness of the washed material, wasin this case, where 2.0 bound acetyl groups per atom of active oxygenwere used, 41%.

EXAMPLE XIII A similar washing test as described in Example I wascarried out using suds containing 753 mg. N-acetyl phthalimide per litreinstead of tetra-acetyl hydrazine.

The relative improvement, as to the lightness of the washed material,Was in the case, where 1.25 bound acetyl groups per atom of activeoxygen were used, 136%.

EXAMPLE XIV Pieces of cotton fabric were soiled as described in ExampleI. After drying in the air, rinsing thoroughly with water and dryingagain, the lightness of the pieces of fabric, measured with aphoto-electric remission meter was 53% of the lightness of magnesiumoxide freshly condensed from the atmosphere.

Seven lots of these pieces of material were washed for minutes at 60 C.in seven diiferent suds.

All these suds contained:

Sodium salt of dodecyl benzene sulphonic acid 0.85 Laurylisopropanolamide 0.10 Tetrasodium pyrophosphate 0.75 Pentasodiumtripolyphosphate 0.60 Alkaline water-glass (Na O/SiO /2) 0.20

NaCMC (100%) (sodium carboxymethylcellulose) 0.040

Sodium sulphate 0.80

All concentrations refer to the anhydrous substances.

Further components of the different suds were as follows.

Suds 1: Sodium perborate (10.0% active oxygen) 0.52 Suds 2:

Sodium perborate 0.50 N,N tetra acetylmethylene diamine (hereinafterreferred to as TAMD) 0.40

bound acetyl groups 2 4 Ratio atoms active oxygen Suds 3:

Sodium perborate 0.40 TAMD 0.40

Ratio bound acetyl groups 30 atoms active oxygen Suds 4:

Sodium perborate 0.40 TAMD 0.30

bound acetyl groups 25 Ratio atoms active oxygen bound aeetyl groupsRatio atoms active oxygen After washing, rinsing and drying, thelightness of the pieces of material was measured.

The results were:

Suds N0 1 2 3 4 5 6 7 Lightuess (percent of MgO) 62 81 79 79 76 76 71.5Difference with the washing-test without TAMD 0 19 17 17 14 14 9. 5Relative improvement,

percent 0 210 190 190 155 155 105 V The relative improvement isexpressed as percentages of the diflFerence in lightness between thepieces of material washed with 0.52 g./l. perborate without TAMD, andthe pieces of material only rinsed with water (lightness 53).

In spite of the very considerable decrease in perborate content of someof the suds, great improvements in bleaching effect were obtained whenTAMD was addedto the suds.

EXAMPLE XV A detergent in powder form was made up having the followingcomposition:

of sodium soap,

of sodium carbonate, of neutral water-glass, of water.

Subsequently five mixtures were prepared, namely:

Mixture 1:

parts by weight of above-mentioned detergent 10 parts by weight ofsodium perborate (9.7% active oxygen) Mixture 2:

85.9 parts by weight of above mentioned detergent 8.6 parts by weight ofsodium perborate 5.5 parts by weight of TAMD Ratio bound acyl groups :20

atoms active oxygen Mixture 3:

87.1 parts by weight of above-mentioned detergent 8.7 parts by weight ofsodium perborate 4.2 parts by weight of TAMD bound acyl groups Ratioatoms active oxygen Mixture 4:

88.5 parts .by weight of above-mentioned detergent 5.8 parts by weightof sodium perborate 5.7 parts by weight of TAMD bound acyl groups Ram)atoms active oxygen 9 Mixture V 91.0 parts by weight of above-mentioneddetergent 4.6 parts by weight of sodium perborate 4.4 parts by weight ofTAMD A detergent was made up having the following composition: PercentSodium salt of dodecyl benzene sulphonic acid 22.4

5 Lauryl isopropanolamide 2.6 Tetrasodium pyrophosphate 20.0 Ratio boundacyl groups Pentasodiurn tripolyphosphate 15.8 ato a ti e xygen Alkalinewater-glass (Na O/SiO /2) 5.1 Sodium carboxymethylcellulose (NaCMC)(100%) 1.0 0 Sodium sulphate 2l.O These mixtures were used inconcentrations of 6.9; Water 12.1 7.2; 7.1; 7.0 and 6.8 g./l.respectively.

In this way, the following concentrations were obtained quently fourmixtures Were prepared, namely: (in g./l.). Mixture l:

85.5 parts by weight of above-mentioned detergent 14.5 parts by weightof sodium pyrophosphate perhydrate (8.05% active oxygen)- Mixture No 1 23 i 4 5 Mixture 2: v sodium Soap 31 31 3.1 3-1 3.1 p 77.9 parts bywelght of above-mentioned detergent Sodium carbonate..- 1.0 1.0 1.0 1.01.0 Parts y Welght 0f sodlllm py p p e pera-a 8- s-a 8'1; 81 hydrateTidt15 i ffff:::::::::3:: 0' 0:40 0136 0:40 0:30 parts y weight of TAMDMixture 3:

91.2 parts by weight of above-mentioned detergent 8.8 parts by Weight ofsodium percarbonate 14.6% Five lots of pieces of cotton material, soiledwith the active Oxygen) same black currant juice as in Example XIV, werewashed Mixture 4; these Suds r 10 mlnptes at After Washms, 82.7 parts byweight of above-mentioned detergent rinsing and drying, the lightness ofthe pieces of mate- 7.8 parts by weight of sodium percarbonate rial wasmeasured, which gave the following results: 95 parts by Weight f A Thesemixtures were used in concentrations of 4.45, 4.88, 4.16 and 4.59 g./l.respectively. To each of the suds, a quantity of oxygen bleaching agentwas added Mlxture N0 1 2 3 4 5 which corresponded to 52 mg./l. of activeoxygen. t f1\ I 0) 62 5 75 6 5 7 655 q .conta'lned the components theorlglnal Difierence wgh the washing-testwith- 0 4 7 5 3 0 detergent 1nthe same concentrations.

t'rAw 12.5 .0 g movements, percent 0 208 67 125 J Walior the TAMDcontaining mlxtures 2 and 4, the ratio Bound acyl groups The relativeimprovement 1s expressed as percentages {F oxygen of the difierence 1nlightness between the pieces of material washed with 0.69 g./l. ofperborate without TAMD (mixture 1) and the pieces of material onlyrinsed with After Washing, rinsing and drying, the lightness of thewater (lightness 56.5 V pieces of material was measured.

In spite of the very considerable decrease in perhorate The resultswere: 1

Mixture No .1 2 3 g 4 Oxygen releasing substance. PyrophosphatePyrophosphate Percarbon- Percarbonperhydrate. perhydrate. 7 ate. ate.Addition TAMD TAMD. Lilg/litgess (percent of '62 80 V g 61 79. Difiel'enee with the ,wash- 0 12 n 18.

ing-test without TAMD. Relative improvement--. 0 190 0 212%.

content of some of the suds, great improvements in bleaching eliect wereobtained when TAMD was added to the suds.

EXAMPLE XVI The relative improvement caused by-TAMD is ex: pressed as apercentage of the dilference in lightness between the'pieces" ofmaterial'washed with the mixture containing the same oxygen bleachingagent without TAMD, and the pieces of material only rinsed with water(lightness 52.5 7

7 EXAMPLE XvrI g g A detergent in powder form had the followingcompositionz 4 7 50.7%.of sodium soap "16.1% of sodium carbonate 2.8% ofneutral water-glass 30.4% ofwater Subsequently four mixtures wereprepared, namely:

Mixture 1:

88 parts by weight of above-mentioned detergent 12 parts by weight ofsodium pyrophosphate perhydrate (8.1% active oxygen) Mixture 2:

82.6 parts by weight of above-mentioned detergent 11.3 parts by weightof sodium pyrophosphate perhydrate 6.1 parts by weight of TAMD Mixture3:

93 parts by weight of above-mentioned detergent 7 parts by Weight ofsodium percarbonate (14.6%

active oxygen) Mixture 4:

87 parts by weight of above-mentioned detergent 6.6 parts by weight ofsodium percarbonate 6.4 parts by Weight of TAMD For the TAMD-containingmixtures 2 and 4, the ratio was:

Bound acyl groups Atoms active oxygen These mixtures were used inconcentrations of 6.9, 7.35, 6.53 and 6.98 g./l. respectively. To eachof the suds, a quantity of oxygen bleaching agent was added whichcorresponded to 67 mg./l. active oxygen.

All suds contained the components of the original detergent in the sameconcentrations.

Four lots of pieces of cotton material stained with the same blackcurrant juice as described in Example I were washed in these suds for 10minutes at 60 C. After washing, rinsing and drying, the lightness of thepieces of material was measured, which gave the follow- The coatingamounted to 25% of the weight of the tetra-acetyl methylenediamine andconsisted of a technical eutectic mixture of stearic and palmitic acid(M.P. 5355 C.). The experiments. were performed at 50 C.

The relative improvements as to the lightness of the washed material,were in these cases, where 2.0 bound acetyl groups per atom of activeoxygen were used respectively 86% and 103%.

When applying a covered tetra-acetyl methylene diamine, an increase inlightness of about 20% as compared with the non-covered compound wasobtained.

When applying 275 mg. of tetra-acetyl hydrazine covered with 18% ofcarboxy-methylcellulose or 428 mg. of tetra-acetylethylenediaminecovered with 9% of cetylalcohol an increase in lightness of respectively29% and 25% as compared with the corresponding non-covered compounds wasfound. Also in these cases the ratio Bound acetyl groups Atom of activeoxygen EXAMPLE XX EXAMPLE XXI was 2.0

Each of four different detergent compositions A, B, C and D contained:

lug results: 12% non 1omc detergent (1sononylphenolpolyglycol- MixtureNo 1 2 3 4 Oxygenreleasingsubstanee. Pyrophosphnte PyrophosphatePercarbon- Percarbonperhydrate. perhydrate. ate. a Addition TAMD TAMD.Lightness (percent of 627 78 60.5 73.

MgO Difiference with the wash- 0 16 0 12.

ing-test without TAMD. Relativeimprovement 0 200% 0 192%.

The relative improvement caused by TAMD is expressed as percentages ofthe difference in lightness between the pieces of material washed withthe mixture containing the same oxygen bleaching agent without TAMD, andthe pieces of material only rinsed with water (lightness 54).

EXAMPLE XVIII EXAMPLE XIX In order to illustrate the beneficial effectof covering an activator according to the invention with a solidmaterial soluble in the washing and/ or bleaching liquid, twocomparative washing tests were carried out as described in Example Iusing suds, containing 0.61 g. of sodium perborate (9.9% of activeoxygen) instead of 0.68 g. per litre, and respectively 401 mg.tetra-acetyl methylenediamine and 401 mg. of the same compound butcovered with a stearic-palmitic acid coating, per litre.

ether, containing about 8 ethylene oxide groups in each molecule) 36%sodium tripolyphosphate 8% sodium silicate, SiO /Na O ratio=2/ l 2%commercial CMC, containing 50% sodium salt. of

carboxymethyl-cellulose 6.6% sodium perborate Further these fourcompositions contained respectively:

Composition A: 4.12% tetra-acetylhydrazine Composition B: 4.40%tetra-acetylmethylenediamine Composition C: 5.50% coatedtetra-acetylmethylenediamine, containing tetra-acetylmethylenediamine asdescribed in Example XIX Composition D: no additional substances In allfour compositions the balance was sodium sulphate. In compositions A, Band C the ratio:

Total meq. combined acyl groups Mg. at. active oxygen was equal to2.021.

All four compositions were used in a concentration of 5.00 g./l. forwashing pieces of a cotton fabric, which had been soiled uniformly withblack currant juice. After thoroughly rinsing with water, and ironing,the lightness (or apparent luminosity) of the fabric was 49.4 (lightnessof magnesium oxide=).

Pieces of this fabric were used for washing with the four detergentcompositions A, B, C and D. After three times rinsing and ironing, theirlightness was measured The results are shown in the following table.

Lightness of fabric pieces, washed and bleached in composition 14 to thebleaching liquid. At 20 the pH of this solution was 10.0.

After the bleaching process, the pieces of cotton fabric were rinsedwith softened water and dried.

Temperature of treatment 5 Measuring with the photo-electric remissionmeter gave A B O D the following remission-values:

g i tBlezitching Temp" Tristimulus leIIllSSlOll values Yrellggv 66.3 67.68.3 mem G B A In the following table, the improvements in the light- 6079.5 67.8 82.5 18.3 ness, caused by the above-mentioned activators areex- 2%: 2 ggressed as percentages of the difference between thelightness of the fabric after rinsing with water only and the lightnessof the material after treatment with detergent While by bleaching withhydrogen peroxide without composition D at 50 C., as compared with thelightness TAMD the yellowness calculated according to the formula of thelatter. from Hunter had hardly altered or even had somewhat 2 increased,by bleaching in the presence of TAMD it de- Percentage improvement oflightness. 0 creased consifierably- Temperature of treatment Treatmentcompomwn- Expressed in percentages of the diiference between theremission values of the piece of fabric bleached accord- A B C D ing totreatment (a) and those of the unbleached sample M, the improvements ofthe remission values of the 3% treated materials, as compared with thoseof the fabric 90 79 96 bleached according to treatment (a) were: 54 6572 Percentage Improvements The same results are obtained, if thedetergent compon sitions contain fluorescent brighteners, dyestuffsand/or Tristimulus-lemission Values perfumes. Essentially the sameresults are obtained with Bleachmg treatment if? other kinds of fabrics,like wool, linen, silk, viscose rayon, G B A acetate rayon, polyamide,polyester, polynitrile, polyvinyl and other natural and syntheticfibres. The same applies 0 0 0 82 19 59 16 to the use of other non ionicsurface active agents and 133 487 173 other builders.

EXAMPLE XXII Pieces of unbleached cotton fabric were boiled for 3 hoursin a 1% solution of sodium hydroxide in water which had been softened bymeans of a cation-exchanger. Thereupon they were rinsed with softenedwater till the sodium hydroxide was almost fully eliminated. Asample ofthe treated fabric was dried (sample M) and the light remissions(difiuse reflections) were measured with the aid of a photo-electricremission-meter. The lightness (G) was 75.9% and the tristimulus blueand amber-remissions (B and A) were 65.6 and 78.8% respectively fromthose of magnesium oxide freshly precipitated from the vapour phase.

The yellowness, J, was 17.1 according to the formula from R. S. Hunter(Photoelectric Tristimulus Colorim etry With Three Filters, Circular ofthe National Bureau of Standards C 429, US. Government Printing Office,Washington, 1942, p. 22):

The pieces of cotton fabric boiled with sodium hydroxide and rinsed withsoftened water were bleached for 15 minutes in the following ways:

(a) At 60 with a solution containing 3.0 g. of anhydrous soda and 2.0 g.of sodium bicarbonate per litre and a quantity of hydrogen peroxideequivalent to an active oxygen content of 1.18 g. per litre of solution.At 20 the pH of the solution was 10.0;

(b) At 82 with a bleaching liquid of the'same composition as thatmentioned under (a). At 20 the pH of this solution was 10.0;

(0) At 60 with a bleaching liquid of the same composition as describedunder (a) and (b) but containing in addition 7.9 g. of TAMD(tetra-acetyhnethylenediamine) and 2.62 g. of sodium hydroxide perlitre. Thus a quantity of TAMD equivalent to 2 meq. acyl groups of TAMDper mg. at. active oxygen was added Consequently the improvements byadding TAMD at 60 were 8 to 10 times as great as the improvements byincreasing the temperature from 60 to 82 without TAMD.

The pieces of cotton fabric bleached according to method (c) containedconsiderably less seedrests than the pieces bleached according to themethods (a) and (b). Moreover, the cotton piece bleached in the presenceof TAMD at 60 was much more hydrophilic than both other ones. A drop ofwater put on it was absorbed immediately.

EXAMPLE XXIII A piece of unbleached cotton fabric was boiled for 1 /2hours in a 1% solution of sodium hydroxide in water softened by means ofa cation-exchanger. Subsequently it was boiled another 1 /2 hours inanother, fresh 1% solution of sodium hydroxide in softened water.There-Z upon it was rinsed with-softened water till the sodium hydroxidewas almost fully eliminated. A sample of the treated cotton fabric wasdried (sample N) and the lightremissions (diffuse reflections) weremeasured with the aid of a photo-electric remission-meter. The lightness(G) and the tristimulus blue and amber remissions (B and A) were; 79.4,73.3 and 81.3 respectively. Conse quently, the yellowness according tothe formula from Y i R. S. Hunter was 10.0.

I Various parts of. the piece of cotton fabric boiled with peratures'andthe results of the measurements are indi cated in the following table.

,a l o l 6 Composition of the bleaching liquidTristimulus-remission-values Percentage improvements of the Temp, End pHYellow- Neutral ness J 30% H201, water, NaOH, TAMD, G B A Light-YellowmL/l. g./l. g./l. g./l. ness G ness .1

0 0 50 8.0 82.2 75. 4 83. 4 9.6 0 0 0 0. 53 3 78 50 5. 1 85. 9 80. 7 8G.0 6. 1 132 875 2. 14 0 0 50 9. 8 84. 0 76. 7 84. 2 8.8 64 200 2. 14 3.18 3. 78 50 9. 6 86. 7 82. 3 86. 6 4. 9 161 1, 175 0 0 0 82 7.6 86. 882. 0 8G. 9 5.6 164 1,000 0 0. 98 3, 78 82 5. 0 88. 0 84. 88. 0 3. 9 2071, 425 2. 14 0 0 82 9. 7 86. 6 81. 6 86. 8 6. 0 157 900 2. 14 3. 1O 3.78 82 9. 0 88. 2 84. 7 87. 9 3. 6 214 1, 500

The improvements as to the remission-values and the yellowness of thebleached cotton fabrics are expressed in percentages of the differencebetween the corresponding values of the unbleached sample N and those ofthe piece of cotton fabric bleached without TAMD and without waterglassat 50 C., as compared with those of the latter.

The improvements due to the presence of TAMD in the bleaching liquidwere most significant both at 82 and at 50 without and with waterglass.All pieces of cotton fabric bleached in the presence of TAMD do notcontain any seedrests, in contrast to the cotton pieces bleached withoutTAMD.

In these tests, a quantity of TAMD equivalent to 0.75 meq. acyl groupsof TAMD per mg. at. of active oxygen was present in the bleachingliquid. The concentrations of active oxygen and TAMD may be chosen bothhigher and lower whereby it is not necessary to stick to the value 0.75for the above-mentioned ratio.

EXAMPLE XXIV On measuring with a photo-electric remission meter, awoolen fabric gave the following light remission values: lightness (G)72.3; tristimulus blue and amber remission (B and A) 57.7 and 74.8respectively. Thus the yellowness (J) according to R. S. Hunter was:23.5. Two parts of this fabric were bleached for 45 minutes at 35 inwater softened with the aid of a cation-exchanger. Thereafter they wererinsed with softened water, dried and their light remission values weremeasured again.

The improvements of the remission values and the yellowness areexpressed again in percentages of the difference between thecorresponding values of the unbleached fabric and those of the fabricbleached according to treatment a, as compared with those of the latter.So by using TAMD in the bleaching liquid, it is clear that the woolenfabric was bleached better.

The concentrations of active oxygen and TAMD may be chosen both higherand lower, whereby it is not necessary to stick to the ratio between theactive oxygenand activator-concentrations given above.

Instead of hydrogen peroxide in the Examples XXII- XXIV other compoundsreleasing active oxygen may be used, such as perborate, percarbonate,pyrophosphate-perhydrate. Instead of TAMD, also other activating agentsaccording to the invention may be used. The duration of the bleachingtreatment may be chosen dependent on the bleaching and the activatingagent concentrations, the temperature, the pH of the bleaching liquidand the improvement required. If desired a surface active substance maybe added so as to accelerate wetting the fabric.

EXAMPLE )OCV Pieces of cotton fabric, soiled with the juice of blackcurrants as described in Example I, were treated according to one of thefollowing three processes.

A. Washing for 10 minutes at 50 C. in suds containing:

Sodium soap 1.00 Sodium CMC 0.10 Sodium carbonate anhydrous 3.86 Neutralwaterglass (100%) 0.36

After washing, the material was rinsed twice with water, first for 10minutes at 50 C., subsequently for 3 minutes at 20 C.

B. Washing and bleaching for 10 minutes at different temperatures insuds of the same composition as described under A, but containing inaddition:

G./l. Sodium perborate (10.2% active oxygen) 0.500Tetra-acetylmethylenediamine 0.335

G./l. Sodium perborate (10.2% active oxygen 0.500Tetra-acetylmethylenediamine 0.335

After this treatment the material was rinsed for 3 minutes at 20 C.

The lightness of the treated material is disclosed in the followingtable.

Process U A 13 0 Temperature of test in C 50 35 50 60 35 50 60 Lightnessof treated material in units 58 65 70 68 66 73 75 Lightness ofmagncsiu1noxide=100 units.

Of the above described acylated activator compounds,

a preferred group are those compounds having the formula:

000E; X-N

COOH:

1 7 wherein X is selected from the group consisting of phenyl, analiphatic acyl group having 1 to 6 carbon atoms in the aliphatic chain,a lower alkyl, a

group in which R represents a lower alkylene group, and R is selectedfrom the group consisting of hydrogen and acetyl, and a 0 on; where R isas defined above.

EXAMPLE XXVI The tetraand tri-acetyl methylenediamine or mixtures ofthese compounds used in the experiments as described in the ExamplesXIV-XIX and XXI-XXV were prepared as follows:

Preparation of N,N'-Tetra-Acetylmethylenediamine A. 200 g. ofN,N'-diacetyhnethylenediamine, which may be prepared from acetamide andparaformaldehyde, were suspended with stirring in 1500 cc. dry benzene.After addition of 4 g. p-toluene-sulphonic acid as a catalyst, ketenewas introduced until all the N,N'-diacety1- methylenediamine had goneinto solution which occurred within 7 hours, at 5065 C. Thereupon, thereaction mixture Was cooled in ice; 159 g. of TAMD crystallized;melting-point 95-96 C. By concentrating the mother liquor to one fourthvolume and cooling, another 137 g. of tetra-acetylmethylenediamine wereobtained.

B. 325 g. (2.5 mols) N,N-diacetylmethylenediamine (M.P 200-200.5 C.) isdissolved by heating in 1530 g. (15 mols) acetic acid anhydride (98%).With the help of a fractionating column the acetic acid formed duringthe reaction is dis-tilled off simultaneously at a bottom temperature of140145 C. in a period of 14 hours.

The reaction comes to an end when the distillate has reached the boilingpoint and refractive index of pure acetic acid anhydride.

The distillate amounting to 425 g. contains 330 g. acetic acid.

By distillation under reduced pressure all the acetic acid anhydridestill present in the reaction mixture is removed yielding 523 g. crudeproduct (theor. 535 g.).

After recrystallization from 523 cc. isopropyl alcohol 480 g. (=2.25mols) pure tetra-acetylmethylenediamine, M.P. 9596 C., is obtained.

Preparation of N,N,N-Tri-A cetyln'zethylenediamine 325 g. (2.5 mols)diacetylmethylenediamine (M.P. 200200.5 C.) is dissolved by heating in3060 g. (30 mols) acetic acid anhydride 98%. After boiling under refluxfor 4 hours the acetic acid/acetic acid anhydride mixture is removedunder reduced pressure yielding 433 g. of a slowly crystallizingproduct. By recrystallization from 433 cc. isopropyl alcohol 359 g.(2.09 mols) of tri-acetylmethylenediamine (MP. 8384 C.) is obtained.

Preparation of a Mixture of T riand T etra-A cetylmethylenediamine 325g. (2.5 mols) diacetylmethylenediamine (M.P. 200-200.5 C.) is dissolvedby heating in 1530 g. (15 mols) acetic acid anhydride 98%.

With the aid of a fractionating column 160 g. of acetic 18 acid isdistilled off during the reaction at a bottom temperature of -145 C. in4 hours.

From the reaction mixture the solvents are distilled off under reducedpressure yielding 490 g. crude product containing besidestri-acetylmethylenediamine also tetraacetylmethylenediamine.

By fractional distillation under reduced pressure 148 g.tri-acetylmethylenediamine, BP. 129-131 C. at 2 mm. Hg and 301 g.tetra-acetylmethylenediamine, BR 138- 140 C. at 2 mm. Hg could beisolated from the crude product.

The invention is not limited by the above-mentioned examples, as withinthe scope of the invention various modifications will be possible. Theactivators may, e.g., successfully be employed in dishwashing agentswhich contain besides an anionic or a cationic or a non-ionicsurface-active substance, also an active oxygen releasing compound, sothat colfee, tea, chocolate, lipstick and similar spots may be removedmore easily. It will also be possible to incorporate the activators in,e.g., bottlewashing agents, in agents for cleansing breweries, dairy andother food-processing factories, etc., Whenever these agents contain anactive oxygen releasing compound.

What is claimed is:

l. A textile treating composition consisting essentially of an activeoxygen releasing compound selected from the group consisting ofinorganic perborates, percarbonates, perphosphates, persilicates,persulfates, and peroxides and an activator compound selected from thegroup consisting of N,I l,NN'-tetra-acetyl hydrazine and N,N,NN'-tetraacetylmethylenediamine, the said activator compound beingpresent in such a quantity as corresponds to 0.54.0 nitrogen boundacetyl groups per atom of active oxygen in the active oxygen releasingcompound.

2. A composition according to claim 1 wherein said active oxygenreleasing compound is sodium perborate.

3. A composition according to claim 1 wherein said activator compound isN,N,N'N-tetra-acetyl hydrazine.

4. A composition according to claim 1 wherein said activator compound isN,N,N'N'-tetra-acetylmethylenediarnine.

5. A composition according to claim 1 wherein said activator is infinely divided form covered with 130% of its weight by a materialselected from the group consisting of stearic acid, a solid polyethyleneglycol having an average molecular weight of 3000-3700, a solidpolyethylene glycol having an average molecular weight of 60007500,carboxymethylcellulose and cetyl alcohol.

References Cited by the Examiner UNITED STATES PATENTS 1,950,956 3/34Wilhelm 252--187 2,267,685 12/41 Kyrides 260561 XR 2,445,319 7/48Engelbrecht 260 --561 XR 2,742,501 4/56 Kleine et a1. 260562 2,838,4596/58 Sprout 252186 2,898,181 8/59 Dithmar et a1. 25299 XR 2,923,738 2/60Williams et al 260-561 2,927,082 3/60 Young 252186 2,932,667 4/ 60Welcher 260561 3,061,550 10/62 Baevsky 25299 OTHER REFERENCES BeilsteinsHandbuch der Organischen Chemie, vol. IV (4th Ed), First Supplement,page 416 (1929).

JULIUS GREENWALD, Primary Examiner.

IRVING MARCUS, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3, 163,606 December 29, 1964 Wilhelmus J. C. Viveen et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 9, line 39, the second table, under the column heading "5", line3 thereof, insert 5O column 12, line 12, for "275" read 375 columns 15and 16, the first table, under the column heading "B", line 6 thereof,for "84.5" read 84.6 same column 15, EXAMPLE XXIV, in the table, underthe column heading "Bleaching treatment b", line 2 thereof, for "9.440"read 9.44

Signed and sealed this 22nd day of June 1965.

(SEAL) Attest:

Commissioner of Patents I UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No. 3, 163 ,606 December 29, 1964 wilhelmus J. c.Viveen et al.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 9, line 39, the second table, under the column heading "5'', line3 thereof, insert 50 column 12, line 12, for "275" read 375 columns 15and 16, the first table, under the column heading "B", line 6 thereof,for

"84.5" read 84.6 same column 15, EXAMPLE XXIV, in the table, under thecolumn heading "Bleaching treatment b", line 2 thereof, for "9.440" read9.44

Signed and sealed this 22nd day of June 1965.

(SEAL) Attest:

ERNEST W. SWIDER' EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. A TEXTILE TREATING COMPOSITIN CONSISTING ESSENTIALLY OF AN ACTIVEOXYGEN RELEASING COMPOUND SELECTED FROM THE GROUP CONSISTING OFINORGANIC PERBORATES, PERCARBONATES, PERPHOSPHATES, PERSILICATES,PERSULFATES, AND PEROXIDES AND AN ACTIVATOR COMPOUND SELECTED FROM THEGROUP CONSISTING OF N,N,N''N''-TETRA-ACETYL HYDRAZINE AND N,N,N''N''-TETRA-ACETYLMETHYLENEDIAMINE, THE SAID ACTIVATOR COMPOUND BEINGPRESENT IN SUCH A QUANTITY AS CORRESPONDS TO 0.5-4.0 NITROGEN BOUNDACETYL GRUPS PER ATOM OF ACTIVE OXYGEN IN THE ACTIVE OXYGEN RELEASINGCOMPOUND.